Synergistic anti icing composition

ABSTRACT

SYNERGISTIC ANTI-ICING COMPOSITION OF (1) POLYMERIC REACTION PRODUCT OF ALIPHATIC MONOAMINE AND EPIHALOHYDRIN COMPOUND AND (2) POLYHYDROXY ALCOHOL.

United States Patent Int. Cl. C101 1/22 U.S. CI. 44-72 7 Claims ABSTRACTOF THE DISCLOSURE Synergistic anti-icing composition of (1) polymericreaction product of aliphatic monoamine and epihalohydrin compound and(2) polyhydroxy alcohol.

BACKGROUND OF THE INVENTION A serious problem in the operation ofautomobiles is stalling of the engine due to the formation of ice in thecarburetor throttle body and on the throttle plate. As is well known, attemperatures ranging from about 30 to about 60 F. and at periods ofrelatively high humidities, such stalling has been encountered underidling or low load conditions. This is caused by the air-borne moistureundergoing freezing due to the refrigerating effect encountered innormal fuel vaporization within the carburetor. The ice formed on thethrottle plate and adjacent carburetor walls restricts the narrow airopenings and causes engine stalling.

The icing problem is of increasing importance because of the design ofnewer automobiles. For example, present cars do not have a manualthrottle and therefore the operator of the car no longer is able toincrease the idle speed during the warm up period to prevent suchstalling. Furthermore, the increasing use of automatic transmissionsadds to this problem because the idle speed must be kept low to avoidcreeping and, accordingly, the idle speed is not sufficiently fast toavoid stalling due to icing. Still another development which appears toadd to this problem is the increased volatility of commercial gasolines,because more frequent stalling is encountered with the more volatilefuels.

Various methods have been proposed to eliminate the stalling ofautomobile engines, including the use of additives. In one method, analcohol is used but this has the objection of requiring largeconcentrations of the alcohol in order to obtain reasonably satisfactoryanti-icing. In another method various salts have been proposed.

DESCRIPTION OF THE INVENTION It now has been found that a synergisticeffect in reducing stalling due to icing is obtained by utilizing amixture of (1) the polymeric reaction product of a monoamine with anepihalohydrin compound and (2) a polyhydroxyl alcohol.

The polymeric reaction product of an amine with an epihalohydrincompound has been used heretofore as an additive to oils heavier thangasoline or as a means of preventing deposit formation in heatexchangers through which oil is passed. More recently, it has been foundthat the polymeric reaction product serves to reduce deposit formationin carbureted combustion engines. For these uses, however, apparentlythe reaction product formed from a monoamine or a diamine with theepihalohydrin compound are substantially equivalent. In contrast, aswill be shown by the data in the present application, applicant hasfound that such equivalence does not prevail for use as an anti-icingagent and particularly in forming a synergistic mixture.

In one embodiment, the present invention relates to a synergisticanti-icing composition of (1) the polymeric reaction product of analiphatic monoamine with an epihalohydrin compound and (2) a polyhydroxyalcohol.

Patented Sept. 4, 1973 In a specific embodiment, the present inventionrelates to a synergistic anti-icing composition of (1) from about 5% toabout by weight of the polymeric reaction product, formed at atemperature of from about 60 F. to about 300 F., of from about 1 toabout 2 mole proportions of an aliphatic monoamine with from about 1 toabout 1.5 mole proportions of an epihalohydrin compound and (2) fromabout 95% to about 5% by weight of a polyhydroxy alcohol containing fromabout 2 to about 50 carbon atoms and from 2 to about 10 hydroxy groups.

In another embodiment, the present invention relates to gasolinecontaining an anti-icing concentration of the synergistic compositionherein set forth.

As hereinbefore set forth, one component of the syner gistic compositionis the polymeric reaction product of an aliphatic monoamine withepihalohydrin compound. In a preferred embodiment, the aliphaticmonoamine contains from about 4 to about 40 and more particularly fromabout 12 to about 30 carbon atoms. Illustrative preferred amines areprimary alkyl amines including dodecyl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecylamine, nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine,tricosyl amine, tetracosyl amine, pentacosyl amine, hexacosyl amine,heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine,etc. Conveniently the long chain amines are prepared from fatty acids ormore particularly mixtures of fatty acids formed as products orby-products. Such mixtures are available commercially, generally atlower prices and, as hereinbefore set forth, the mixtures may be usedwithout the necessity of separating individual amines in pure state.

An example of such a mixture is hydrogenated tallow amine which isavailable under various trade names including Alamine H26D and ArmeenHTD. These products comprise mixtures predominating in alkyl aminescontaining 16 to 1-8 carbon atoms per alkyl group, although they containa small amount of alkyl groups having 14 carbon atoms.

As hereinbefore set forth, the amine compound is reacted with anepihalohydrin compound. Epichlorohydrin is preferred. Otherepichlorohydrin compounds include 1,2-epoxy-4-chlorobutane,2,3-epoxy-4-chlorobutane, 1,2- epoxy-S-chloro-pentane, 2,3epoxy-S-chloropentane, etc. In general, the chloro derivatives arepreferred, although it is understood that the corresponding bromo andiodo compounds may be employed. In some cases epidihalohydrin compoundsmay be utilized. It is understood that the different epihalohydrincompounds are not necessarily equivalent and that, as hereinbefore setforth, epichlorohydrin is preferred.

The amine is reacted with the epihalohydrin compound in a mole ratio offrom about 1 to about 2 mole proportions of amine and from about 1 toabout 1.5 mole proportions of epihalohydrin compound. The amine andepichlorohydrin preferably are reacted in substantially equal moleproportions.

The reaction of amine and epihalohydrin is effected in any suitablemanner. In one method, the desired quantity of amine and epihalohydrincompound may be charged to a reaction zone and therein reacted, althoughgenerally it is preferred to supply one reactant to the reaction zoneand then introduce the other reactant step wise. Thus, the epihalohydrincompound may be charged to the reaction zone and the amine is added stepwise, with stirring. Preferably, the reaction of epichlorohydrin withthe second or later portions of the amine is effected at a highertemperature than with the first portion of the amine. The reactionpreferably is effected in the presence of a suitable solvent andparticularly a hydroxylic solvent. In a preferred method, a solution ofthe amine in a solvent and a separate solution of the epihalohydrincompound in a solvent are prepared and these solutions then arecommingled in the manner hereinbefore set forth, at least one of thesolvents being hydroxylic. Any suitable solvent may be employed andpreferably comprises an alcohol including ethanol, propanol, butanol,etc., 2-propanol being particularly desirable. Other hydroxylic solventscomprise glycols including ethylene glycol, propylene glycol, etc.,glycerol or other polyhydric solvents.

The reaction of amine compound and epihalohydrin compound is effected atany suitable temperature, which generally will be within the range offrom about 60 to about 300 F. and preferably is in the range of fromabout 120 to about 185 F. Conveniently, this reaction is effected byheating an epichlorohydrin solution in dilute alcohol at refluxingconditions, with stirring, gradually adding the amine thereto, andcontinuing the heating, preferably at a higher temperature, until thereaction is completed, or the reverse order of adding the reactants maybe employed.

After the initial reaction of the amine compound and epihalohydrincompound is completed, the organic halide salt, which inherently isformed, is converted to an inorganic salt, to thereby liberate the freeamine for further reaction to form the desired polymeric product. Thismay be effected in any suitable manner and generally is accomplished byreacting the primary reaction product with a strong inorganic base suchas sodium hydroxide, potassium hydroxide, etc. to form the correspondingmetal halide. The reaction to form the metal halide is effected at atemperature within the range of from about 130 to about 212 F. andpreferably from about 165 to about 195 F. The inorganic base preferablyis added in at least two steps, with intervening heating and reacting,so that organic halide formed after the first addition of inorganic baseis in turn reacted to liberate the free amine.

In one embodiment the product at this stage of manufacture may bewithdrawn from the reaction zone and filtered or otherwise treated toremove the inorganic halide. Generally however, it is preferred toperform the next step in the same reaction zone without removing theinorganic halide. At the conditions used in forming the polymericreaction product, the inorganic halide is inert and, therefore, itspresence is not objectionable. Regardless of whether or not theinorganic halide is removed, the primary reaction product of the aminecompound and epihalohydrin compound is now further heated and reacted inorder to form the desired linear polymeric reaction product. Thisfurther heating and reacting is at a temperature of from about 130 toabout 212 F. and preferably from about 165 to about 195 F.

After formation of the desired polymeric reaction product or before thisstep as mentioned above, the inorganic halide salt is removed in anysuitable manner, including filtering, centrifugal separation, etc. Insome cases, it may be of advantage to effect the filtration at anelevated temperature, which may range from about 95 to about 160 F. ormore.

As hereinbefore set forth, the polymeric reaction product will have from2 to 20 and preferably from 3 to recurring units. The reaction productswill range from liquids to solids and, when desired, may be prepared asa solution in a suitable solvent for ease in handling and using. Apreferred solvent is an aromatic hydrocarbon including benzene, toluene,xylene, ethylbenzene, diethylbenzene, cumene, etc., or a mixed solventsuch as naphtha, kerosene, xylene tower bottoms, etc. In one embodimentall or a portion of the aromatic solvent desired in the final productmay be used as a solvent during the reaction, in addition to thehydroxylic solvent, and the aromatic solvent is allowed to remain in thefinal product.

As hereinbefore set forth, the polymeric reaction prodnot is used inadmixture with a polyhydroxy alcohol. A

preferred polyhydroxy alcohol is the commercially available hexyleneglycol which is 2,4-dihydroxy-2-methylpentane. Other polyhydroxyalcohols include ethylene glycol, propylene glycol, butylene glycol,pentylene glycol, other hexylene glycols as, for example,1,6-dihydroxyhexane, 2,6-dihydroxyhexane, etc., heptylene glycol,octylene glycol, etc., diethylene glycol, dipropylene glycol, dibutyleneglycol, tributylene glycol, etc., dihydroxycyclohexane as, for example,1,4-dihydroxycyclohexane, 1,3-dihydroxycyclohexane,l,Z-dihydroxycyclohexane, etc., glycerol, 1,2,3-butanetriol,pentanetriol, hexanetriol, heptanetriol, erythritol, etc. In a preferredembodiment the polyhydroxy alcohol is a dihydroxy alcohol containingfrom 2 to 8 carbon atoms and may be of straight or branched chain.However, it is understood that the polyhydroxy alcohol may contain 3 ormore hydroxy groups, generally not above about 10 hydroxy groups, aswell as being of aliphatic or cyclic in configuration.

In another embodiment, the polyhydroxy alcohol is an alkylene oxideaddition product of a polyol. The alkylene oxide may comprise ethyleneoxide and preferably propylene oxide, although it may comprise butyleneoxide, amylene oxide, hexylene oxide etc. The polyol may compriseethylene glycol, propylene glycol, butylene glycol, amylene glycol,hexylene glycol, etc., trimethylene glycol, tetramethylene glycol,pentamethylene glycol, hexamethylene glycol, etc. Triols include pentanetriol, hexane triol, heptane triol, octane triol, etc. Other polyols maycontain from 4 to 10 hydroxyl groups and thus will include thecarbohydrates, including particularly sorbitol.

A number of the polyhydroxy alcohols prepared via alkylene oxideaddition are available commercially. One of these is a polyoxypropylenepolyol available commercially as NIAX LET-240 and is prepared by thereaction of a hexane triol with propylene oxide. Analysis shows theproduct to have a hydroxy number of 234.6, which corresponds to about 10moles of propylene oxide per mole of hexane triol. Accordingly, thispolyhydroxy alcohol contains an average of 36 carbon atoms and 3hydroxyl groups. Another such product is available commercially as NIAXLHT-550 and is believed to be the mixed polyol resulting from thepropylene oxide addition to a mixture of hexane triol and sorbitol. Thispolyhydroxy alcohol is said to have a hydroxyl number of about 550, anacid number of 0.2 maximum and a specific gravity 20/20 of 1.0910.

While the polyhydroxy alcohols prepared via alkylene oxide additionconveniently are obtained commercially, when desired these may beprepared in any suitable manner. In general, a polyhydroxy hydrocarbonis reacted with an alkylene oxide, including particularly ethylene oxideand propylene oxide, in molar ratios to produce the oxyalkylatedpolyhydroxy hydrocarbon containing the number of oxyalkane groupsdesired. These may range from 1 to 20 and preferably from 5 to 15. Theoxyalkylation is effected in any suitable manner and generally will beconducted at a temperature of from about room temperature to about 350F. and more particularly from about 200 F. to about 300 F., preferablyin the presence of a catalyst such as sodium hydroxide, potassiumhydroxide, tertiary amine, quaternary hydroxide, etc. When theoxyalkylation is to be limited to the addition of one oxy group, thecatalyst may be omitted and the reaction is effected in the presence ofwater. Superatmospheric pressure may be employed, which may range from10 to 1000 pounds or more.

When desired, a mixture of polyhydroxy alcohols is employed.Illustrative mixtures include a mixture comprising from to by weight ofhexylene glycol and 5% to 15% by weight of glycerol, a mixture of 75% to95% by weight of ethylene glycol and 5% to 25% by weight of erythritol,etc. Also when desired, a mixture of monoamines and/or of epihalohydrincompounds may be used in preparing the polymeric reaction product.

These compounds will be selected from those hereinbefore set forth.

The polymeric reaction product and polyhydroxy alcohol will be used insuitable proportions, which may range from about to about 95% andpreferably from to 90% by weight of the polymeric reaction product andfrom about 95 to about 5% and preferably from 90% to 10% by weight ofthe polyhydroxy alcohol.

The amount of total anti-icing composition to be added to the gasolinewill be sufficient to effect improved deicing. For economic reasons, theconcentration should be as low as practicable and may range from 0.0001%to 0.05% by weight and preferably is within the range of from about0.002% to about 0.01% by weight of the fuel, based on the mixedpolymeric reaction product and polyhydroxy alcohol exclusive of solventwhen employed. While each of the polyamine and the polyhydroxy alcoholmay be added separately to the fuel, it generally is pre ferred toprepare a composition of the polymeric reaction product and polyhydroxyalcohol in the proper concentrations and to add this composition to thefuel in the desired amount. When desired, the mixture of polymericreaction product and polyhydroxy alcohol may be prepared as a solutionin a suitable solvent which may comprise a paraffinic, aromatic and/ ornaphthenic naphtha or gasoline. When desired, the solvent may comprisean aromatic or paraffinic hydrocarbon, including benzene, toluene,xylene, ethylbenzene, etc., pentane, hexane, heptane, octane, etc. Whena solvent is used, the polymeric reaction product and hexylene glycolwill comprise from about 10% to about 90% and preferably from about 25%to about 75% of the solution.

The synergistic composition of the present invention may be used in anygasoline. Commercial gasolines generally comprise a mixture of two ormore of cracked gasoline, hydrocracked gasoline, reformed gasoline,alkylate, isoparafiins, aromatics, etc., and in some cases may containstraight run gasoline, coker distillate, etc. It is understood that thesynergistic composition of the present invention may be used along withother additives incorporated in gasoline. These may include antioxidant,metal deactivator, tetra-alkyl lead, detergent, dye, etc. When desired,one or more of these additional additives may be admixed with thecomposition of the present invention and marketed and used in thismanner.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

EXAMPLE I A polymeric reaction product is prepared by the reaction ofone mole proportion of epichlorohydrin with one mole proportion ofhydrogenated tallow amine. It will be noted that the hydrogenated tallowamine comprises a mixture which predominates in alkyl amines containing16 to 18 carbon atoms per alkyl group although they contain a smallamount of alkyl group having 14 carbon atoms. In one method, thereaction is effected by first forming a solution of 2 moles ofepichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. ofxylene and 200 cc. of 2-propanol. A separate solution of 2 moles of thehydrogenated tallow amine is prepared in an equal volume of xylene. Onemole of the latter solution is gradually added to the epichlorohydrinsolution, with stirring and heating at l30140 F. for about 2.5 hours,after which another mole of the hydrogenated tallow amine is addedgradually to the reaction mixture, stirred and reacted at 175 F. forabout 2.5 hours. One mole of sodium hydroxide then is added withstirring and heating at 185195 F. for 3 /2 hours, after which anothermole of sodium hydroxide is added to the mixture, stirred and reacted at185-195 F. for about 1 hour.

It will be seen that the heating and reacting after the addition of thesodium hydroxide and concomitant liberation of the free amine results inthe formation of the desired polymeric reaction product. Followingcompletion of the reaction, the mixture is cooled, filtered and thefiltrate is distilled to remove the alcohol. In this preparation thexylene solvent is allowed to remain in the final product and is used inthis manner.

However, for analytical purposes, a portion of the above solution isdistilled at 0.1 mm. of vacuum to remove the xylene and to recover asubstantially pure reaction product. This product is a white toolf-white hard, brittle solid, and has a softening point of about F. andmelts at 124 F. to a dark yellow liquid, which liquid is soluble in allcommon hydrocarbon and other organic solvents. This product has anequivalent weight by titration with acid of 334.

EXAMPLE II It will be noted that in Example I the first mole of tallowamine is reacted with epichlorohydrin at F. and then the second mole oftallow amine is reacted at the higher temperature of F. When effectingthe reaction in this manner, the polymeric product will have a total ofabout 12 recurring units. However, when the reaction of all of theconstituents is effected at substantially the same temperature, thereaction product will contain 5 or less recurring units. A specificpreparation was calculated to comprise 4 recurring units and a molecularweight of about 1400.

EXAMPLE III Another polymeric reaction product is prepared insubstantially the same manner as described in Example I except that theamine is oleylamine. The oleylamine and epichlorohydrin are used inequal molecular proportions and the final product is prepared as a 50%solution in a naphtha solvent.

EXAMPLE IV A synergistic mixture was prepared by mixing the polymericreaction product prepared as described in Example I with hexyleneglycol. The polymeric reaction product previously was formed as a 50%solution in naphtha. The synergistic mixture contained 50% of thepolymeric reaction product solution (25% by weight of active ingredient)and 50% by weight of hexylene glycol.

The anti-icing properties were determined in a carburetor icingdemonstrating apparatus consisting of a vacuum pump equipped so thatcool moisture-saturated air from an ice tower is drawn through asimulated carburetor. The gasoline sample passes from a fuel reservoirthrough a flow meter into the carburetor at a rate of 1.4 lb./hr. Theair from the ice tower is passed at a flow rate of 14.4 lb./hr. at atemperature of 40 F. The manifold vacuum is 9.5 in. Hg at the start and12.5 at the end of the test. Evaporation of the gasoline in thecarburetor further cools the cold moist air, with resulting iceformation on the throttle plate. The time in seconds is measured until adrop of 3 in. Hg vacuum occurs, which indicates stalling conditions.

The fuel used in this example is a commercial gasoline which, withoutanti-icing additive, reached stalling conditions within about 15seconds. The gasoline used in this example was of summer grade and has aslightly lower vapor pressure than winter grade fuels. This accounts forthe fact that the icing time was about 15 seconds rather than about 8seconds which normally is encountered with the winter grade gasoline.

When the polymeric reaction product was used alone in concentrations of25, and 50 and 100 ppm. (parts per million) of solution (12.5, 25 and 50ppm. active ingredient respectively), the stalling times were 37.9, 68and 93.3 seconds respectively. In contrast to the above, a mixture of 50parts by weight of the solution of poly? meric reaction product (25parts active ingredient) and 50 parts by weight of hexylene glycol gavethe following results. When used in a concentration of 50 ppm.(containing only 12.5 parts active polymeric reaction product) thestalling condition was 47.2 seconds which is compared to the stallingtime of 37.9 seconds obtained with an equal concentration of polymericreaction product active ingredient. At a concentration of 100 p.p.m.active ingredient of reaction product) the stalling condition was 109.5seconds which compares to the 68 seconds obtained when using an equalconcentration of the polymeric reaction product active ingredient. Thusthe icing time is increased by 41.5 seconds, which is a considerableimprovement and demonstrates the strong synergistic effect obtained byusing the mixture of ingredients.

Hexylene glycol when used by itself shows only minor benefit inincreasing the icing time.

EXAMPLE V The synergistic mixture of this example is 50% by weight ofthe polymeric reaction product solution, prepared as described inExample I (25% by weight of active ingredient) and 50% by weight of NIAXLHT-240. As hereinbefore set forth, this polyhydroxy alcohol is thepropylene oxide addition product to hexane triol. The NIAX LHT-240 whenused alone, gave the stalling conditions of 15.6 seconds, 17.8 secondsand 18.4 seconds at concentrations of 25, 50 and 100 p.p.m. In contrast,the mixture of 50% polymeric reaction product of Example I in 50%solution (25% active ingredient) and 50% by weight of NIAX LHT-240 gavestalling conditions of 45.5 seconds and 162.8 seconds at concentrationsof 25 and 50 p.p.m. respectively. The 162.8 seconds is compared to thesum of the 17.8 seconds obtained when using 50 p.p.m. of NIAX LHT-240and with the 68 seconds obtained when using 50 p.p.m. (25 p.p.m. activeingredient) of the polymeric reaction product solution. Thus, one wouldexpect to obtain stalling conditions of 17.8 seconds plus 68 seconds or85.8 seconds by using a mixture of these ingredients in theseconcentrations. Instead, a stalling time of 162.8 seconds was obtainedwhich is about double the expected stalling time and dramaticallydemonstrates the strong synergistic elfect obtained by using themixture.

EXAMPLE VI As hereinbefore set forth, the synergistic effect obtainedwhen using the polymeric reaction product appears to apply when amonoamine is used as a reactant. For example, a polymeric reactionproduct was prepared in substantially the same manner as described inExample I except that the amine used was N-tallow-1,3-diaminopropane.When evaluated in the same manner as described in Example IV, a 50%solution of this polymeric reaction product increased the stalling timefrom about 16 seconds in the absence of the additive to 28.3 and 35.9seconds, respectively, at concentrations of polymeric reaction productsolutions (25 and 50 p.p.m. active ingredient) of 50 and 100 p.p.m. Amixture of a 50% solution of this polymeric reaction product (25 p.p.m.active ingredient) and 50% hexylene glycol gave a stalling time of 23.6seconds at a concentration of 100 p.p.m. (25 p.p.m. active polymericreaction product). It will be noted that no synergistic effect wasobtained when using the mixture of polyhydroxy alcohol and polymericreaction product prepared from the diamine.

I claim as my invention:

1. Synergistic anti-icing composition of (1) from about 5% to about 95%by weight of the polymeric reaction product, formed at a temperature offrom about F. to about 300 F., of from about 1 to about 2 moleproportions of an aliphatic monoamine containing from about 4 to about40 carbon atoms with from about 1 to about 1.5 mole proportions of anepihalohydrin compound selected from the group consisting ofepichlorohydrin, 1,2-epoxy-4-chlorobutane, 2,3-epoxy-5-chloropentane,and (2) from about to about 5% by weight of a polyhydroxy alcohol, whichis an alkylene oxide addition product to a polyol.

2. The composition of claim 1 in which said monoamine contains fromabout 12 to about 30 carbon atoms.

3. The composition of claim 1 in which said monoamine is hydrogenatedtallow amine.

4. The composition of claim 1 in which said monoamine is oleylamine.

5. The composition of claim 1 in which said polyhydroxy alcohol is thepropylene oxide addition product to hexane triol.

6. Gasoline containing an anti-icing concentration of the synergisticcomposition of claim 1.

7. Gasoline containing an anti-icing concentration of the synergisticcomposition of claim 3.

References Cited UNITED STATES PATENTS 3,017,258 1/1962 Pollitzer 44723,017,343 1/ 1962 Pollitzer 4472 2,936,223 5/ 1960 Lovett et a1. 44772,722,099 11/1955 Wasserbach 4477 2,807,525 9/1957 Foreman 4477 DANIELE. WYMAN, Primary Examiner V. H. SMITH, Assistant Examiner US. Cl. X.R.44DIG 1, 62

